CN108724822B - Preparation method of electromagnetic shielding honeycomb core material - Google Patents
Preparation method of electromagnetic shielding honeycomb core material Download PDFInfo
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- CN108724822B CN108724822B CN201810425566.7A CN201810425566A CN108724822B CN 108724822 B CN108724822 B CN 108724822B CN 201810425566 A CN201810425566 A CN 201810425566A CN 108724822 B CN108724822 B CN 108724822B
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Abstract
The invention belongs to the technical field of composite materials, and relates to a preparation method of an electromagnetic shielding honeycomb core material. According to the invention, graphene/ferrite hybrid materials are prepared, and graphene/ferrite hybrid particles are uniformly attached to a fabric carrier in a magnetic deposition mode to form the graphene/ferrite hybrid particle electromagnetic shielding fabric. And preparing an electromagnetic shielding interlayer by using the prepreg, the adhesive film and the electromagnetic shielding fabric. And finally, compounding the electromagnetic shielding interlayer and the honeycomb core material into a C interlayer electromagnetic shielding honeycomb structure in a bonding mode. The technical process fully integrates related mature technologies, and realizes low-cost design, manufacturing and technical integration comprehensive utilization of the electromagnetic shielding honeycomb core material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a preparation method of an electromagnetic shielding honeycomb core material.
Background
Nowadays, radio signals are increasing day by day, the electromagnetic spectrum is increasingly dense, and the electromagnetic power density is sharply increased. Therefore, the application of shielding technology in various fields is increasingly important, military aspects are controlled from communication detection satellites to various unmanned detection airplanes to precision guided weapons, civil aspects are controlled from miniature communication tools to various data transmission to satellite digital television signals, and the like, the shielding importance in the aviation field is more prominent, in severe electromagnetic environments, radio frequency energy has great hazard, light people cause discomfort to the bodies of the people, and electronic equipment is reduced. The service performance of the ordnance system causes influence on the accuracy of the equipment, seriously damages the human body, endangers the ordnance and fuel oil containing the electric explosion device, causes the comprehensive paralysis of an airborne electronic system, and more possibly causes the disastrous accidents of the mechanical damage and the death,
therefore, whether electromagnetic protection can be done or not is one of the key technologies related to whether each industry can safely work under the complex electromagnetic field environment or not. The use of electromagnetic shielding materials is one of the most effective ways to achieve electromagnetic shielding. Conventional electromagnetic shielding methods mainly include the use of a metal material or the use of a shielding coating. Although the metal material has good electromagnetic shielding efficiency, the metal material cannot meet the light-weight design requirement of the current aircraft due to the large self weight. The shielding coating treatment on the material surface has the defects of complicated working procedures and influence on the shielding effect due to the falling of the coating. Although the polymer material has the characteristics of good mechanical property, light weight and the like, the design of the electromagnetic compatibility of the airplane is troublesome due to the large radio frequency resistance and poor electric conductivity of the polymer material. The main method of the novel polymer electromagnetic shielding material mainly comprises the steps of adding conductive filler or pre-buried conductive media into a material matrix, wherein the conductive filler can effectively improve the conductive performance of the polymer material, so that the polymer material has the electromagnetic shielding performance, the uniform dispersion of the conductive filler in a material system wastes time and labor, and the material strength is correspondingly reduced along with the increase of the addition amount. The pre-buried conductive medium has the defect of complex working procedures. At present, honeycomb core materials are mainly adopted in the structural members of the aviation airplanes as interlayer materials, and the structural members have the characteristics of light weight, excellent mechanical properties and the like. The honeycomb core material with the electromagnetic shielding effect is reasonably developed in consideration of the large-area use of the honeycomb core structure in the main body structure in the aircraft cabin, so that not only can precise instruments and passengers in the aircraft flight cabin be effectively protected from electromagnetic interference, but also various defects of metal materials, shielding coatings, conductive fillers and conductive medium modified high polymer materials can be reasonably improved.
Disclosure of Invention
The invention aims to provide a preparation method of an electromagnetic shielding honeycomb core material aiming at the defects of the prior art. The technical solution of the present invention is that,
(1) preparing the following raw materials in parts by mass for later use:
0.5-5 parts of graphene, 1000 parts of deionized water and 2200 parts of Fe3+50-600 parts of Fe2+30-200 parts of ammonia water and 10-100 parts of ammonia water;
adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; mixing the above parts by mass of Fe3+，Fe2+Adding the graphene suspension into the graphene suspension, and continuously stirring the graphene suspension in a water bath at the temperature of between 30 and 80 ℃ for 10 to 60 minutes; then adding 10-100 parts of ammonia water by mass, and continuing to stir in a water bath for 10-60 minutes; repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral;
(2) separating the graphene/ferrite particles from deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%;
(3) flatly paving a fabric carrier (carbon nanotube paper, a metal mesh, carbon fiber cloth, graphene paper and non-woven fabric) at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with deposited graphene/ferrite particles;
(4) sequentially placing adhesive films and prepregs (carbon fiber prepregs, glass fiber prepregs and plant fiber prepregs) on two surfaces of the electromagnetic shielding fabric of the graphene/ferrite particles to be pressed into a hard sheet (when the hard sheet is pressed, the layers of the prepregs placed on the two surfaces of the electromagnetic shielding fabric of the graphene/ferrite particles are symmetrical or asymmetrical);
(5) bonding a graphene/ferrite hard thin plate between two honeycombs (aramid fiber paper honeycombs, plant fiber honeycombs and glass cloth honeycombs, the thickness of the honeycombs is 5mm-600mm) by using an adhesive film to prepare a honeycomb sandwich material with electromagnetic shielding performance;
and (5) repeating the step (4) and the step (5) according to the electromagnetic shielding requirement to realize the preparation of the multilayer electromagnetic shielding honeycomb sandwich material.
The invention has the advantages that:
the invention simultaneously realizes the structural and functional integrated design of the aviation core material, integrally improves the space utilization rate of the honeycomb core, and combines the excellent electrical properties of light weight, high conductivity and the like of a graphene and ferrite material system, thereby realizing the purpose of functional development of the honeycomb core.
The graphene/ferrite electromagnetic shielding honeycomb core material prepared by the method is remarkably characterized in that graphene/ferrite hybrid particles are prepared by a hydrothermal method, and the graphene/ferrite hybrid particles are prepared into an electromagnetic shielding carrier through magnetic sedimentation. And placing the film between the prepreg and the adhesive film to prepare the hard sheet. And the honeycomb material is sandwiched between two or more layers of honeycomb material through the adhesive effect of adhesive films. Due to the electromagnetic shielding performance of the graphene/ferrite hard thin plate, the honeycomb has the electromagnetic shielding performance integrally. Compared with the prior art, the method has the following advantages:
(1) compared with a metal electromagnetic shielding material, the graphene/ferrite electromagnetic shielding honeycomb core material has the advantages of structural function integration and light weight;
(2) compared with an electromagnetic shielding coating, the graphene/ferrite electromagnetic shielding honeycomb core material has the characteristics of simple process and low possibility of falling off;
(3) compared with a conductive filler modified high polymer material, the graphene/ferrite electromagnetic shielding honeycomb core material has good mechanical property, subsequent processing and use are not influenced, and meanwhile, the weight of the material is increased a little, so that the material light weight design requirement is met;
(4) compared with the conductive fiber pre-embedded modified high polymer material, the graphene/ferrite electromagnetic shielding honeycomb core material is simple in process by using a C interlayer method, and the preparation requirement can be met by conventional equipment;
(5) compared with the prior art, the graphene/ferrite electromagnetic shielding honeycomb core material prepared by the C interlayer method can control the number of the foam graphene/ferrite hard thin plate interlayers according to the actual electromagnetic shielding requirement, and has more flexible design.
Drawings
FIG. 1 is a flow chart of the present invention (1 prepreg, 2 adhesive film, 3 graphene/ferrite carrier, 4 graphene/ferrite hard sheet)
FIG. 2 is a flow chart of the preparation of the single-layer graphene/ferrite electromagnetic shielding honeycomb core material (5 honeycomb core material, 4 graphene/ferrite hard sheet, 6 single-layer graphene/ferrite electromagnetic shielding honeycomb core material)
FIG. 3 shows the multi-layer graphene/ferrite electromagnetic shielding honeycomb core material (5 honeycomb core material, 4 graphene/ferrite hard sheet, 7 multi-layer graphene/ferrite electromagnetic shielding honeycomb core material)
Detailed Description
The design and preparation techniques of the present invention are further illustrated by the following examples.
(1) 0.5-5 parts of graphene, 1000 parts of deionized water and 2200 parts of Fe3+50-600 parts of Fe2+30-200 parts of ammonia water and 10-100 parts of ammonia water;
adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; mixing the above parts by mass of Fe3+，Fe2+Adding the graphene suspension into the graphene suspension, and continuously stirring the graphene suspension in a water bath at the temperature of between 30 and 80 ℃ for 10 to 60 minutes; then adding 10-100 parts of ammonia water by mass, and continuing to stir in a water bath for 10-60 minutes; and repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral.
(2) Separating the graphene/ferrite particles from the deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%.
(3) The method comprises the steps of flatly paving a fabric carrier (carbon nanotube paper, a metal mesh, carbon fiber cloth, graphene paper and non-woven fabric) at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with the deposited graphene/ferrite particles.
(4) And sequentially placing a plurality of layers of prepregs (carbon fiber prepregs, glass fiber prepregs and plant fiber prepregs) and 1 layer of adhesive film on two sides of the electromagnetic shielding fabric of the graphene/ferrite particles to prepare the hard sheet.
(5) Processing two honeycomb sheets (aramid paper honeycomb, plant fiber honeycomb and glass cloth honeycomb, the thickness of the honeycomb is 5-600 mm), taking the graphene/ferrite hard sheet as an interlayer material, and bonding the honeycomb and the graphene/ferrite interlayer material by using an adhesive film to form the honeycomb interlayer material with the electromagnetic shielding performance.
(6) And (5) repeating the step (4) and the step (5) according to the electromagnetic shielding requirement, so that the preparation of the multi-electromagnetic shielding interlayer honeycomb core material can be realized.
Example 1
A manufacturing technology of a graphene/ferrite electromagnetic shielding interlayer honeycomb core material is characterized in that the design and preparation steps (figure 1 and figure 2) are as follows:
(1) 0.5-5g of graphene, 1000-2200g of deionized water, 50-600g of ferric chloride, 30-200g of ferrous chloride and 10-100mL of ammonia water;
adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; adding the ferric chloride and the ferrous chloride in parts by weight into the graphene suspension, and continuously stirring in a water bath at the temperature of 30-80 ℃ for 10-60 minutes; then adding 10-100g of ammonia water in parts by weight, and continuing stirring in a water bath for 10-60 minutes; and repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral.
(2) Separating the graphene/ferrite particles from the deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%.
(3) Selecting carbon nanotube paper as a fabric carrier, paving the carbon nanotube paper at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with the deposited graphene/ferrite particles.
(4) And (3) placing 3 layers of carbon fiber prepreg and 1 layer of medium temperature adhesive film on one surface of the electromagnetic shielding fabric of the graphene/ferrite particles, and placing 5 layers of carbon fiber prepreg and 1 layer of medium temperature adhesive film on the other surface of the electromagnetic shielding fabric by using a vacuum tank to prepare the hard thin plate.
(5) Processing two aramid paper honeycomb sheets, taking the graphene/ferrite hard thin plate as an interlayer material, and bonding the honeycomb and the graphene/ferrite interlayer material by using a medium-temperature adhesive film to form the honeycomb interlayer material with the electromagnetic shielding performance.
Example 2
A manufacturing technology of a graphene/ferrite electromagnetic shielding interlayer honeycomb core material is characterized in that the design and preparation steps (figure 1 and figure 2) are as follows:
(1) 0.5-5g of graphene, 1000-2200g of deionized water, 50-600g of ferric chloride, 30-200g of ferrous chloride and 10-100mL of ammonia water;
adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; adding the ferric chloride and the ferrous chloride in parts by weight into the graphene suspension, and continuously stirring in a water bath at the temperature of 30-80 ℃ for 10-60 minutes; then adding 10-100g of ammonia water in parts by weight, and continuing stirring in a water bath for 10-60 minutes; and repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral.
(2) Separating the graphene/ferrite particles from the deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%.
(3) Selecting a metal net as a fabric carrier, paving the metal net at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with the deposited graphene/ferrite particles.
(4) And 4 layers of glass fiber prepregs and 1 layer of high-temperature adhesive film are symmetrically arranged on two sides of the electromagnetic shielding fabric of the graphene/ferrite particles by using a press and pressed into a hard thin plate.
(5) Processing two glass cloth honeycomb sheets, taking the graphene/ferrite hard thin plate as an interlayer material, and bonding the honeycomb and the graphene/ferrite interlayer material by using a high-temperature adhesive film to form the honeycomb interlayer material with the electromagnetic shielding performance.
Example 3
Similar to example 1, a manufacturing technique of graphene/ferrite electromagnetic shielding foam is characterized by the following design and preparation steps (fig. 1-3):
a manufacturing technology of a graphene/ferrite electromagnetic shielding interlayer honeycomb core material is characterized in that the design and preparation steps (figure 1 and figure 2) are as follows:
(1) 0.5-5g of graphene, 1000-2200g of deionized water, 50-600g of ferric chloride, 30-200g of ferrous chloride and 10-100mL of ammonia water;
adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; adding the ferric chloride and the ferrous chloride in parts by weight into the graphene suspension, and continuously stirring in a water bath at the temperature of 30-80 ℃ for 10-60 minutes; then adding 10-100g of ammonia water in parts by weight, and continuing stirring in a water bath for 10-60 minutes; and repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral.
(2) Separating the graphene/ferrite particles from the deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%.
(3) Selecting graphene paper as a fabric carrier, paving the graphene paper at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with the deposited graphene/ferrite particles.
(4) And (3) placing 5 layers of plant fiber prepreg and 1 layer of medium temperature adhesive film on one surface of the electromagnetic shielding fabric of the graphene/ferrite particles, and placing 3 layers of plant fiber prepreg and 1 layer of medium temperature adhesive film on the other surface of the electromagnetic shielding fabric of the graphene/ferrite particles by using a press machine, and pressing the electromagnetic shielding fabric into a hard thin plate.
(5) Processing two aramid paper honeycomb sheets, taking the graphene/ferrite hard thin plate as an interlayer material, and bonding the honeycomb and the graphene/ferrite interlayer material by using a medium-temperature adhesive film to form the honeycomb interlayer material with the electromagnetic shielding performance.
(6) And (3) designing the number of interlayers according to the electromagnetic shielding requirement, and repeating the step (4) and the step (5) on the basis of obtaining the single-layer graphene/ferrite electromagnetic shielding honeycomb core material to realize the preparation of the multi-electromagnetic shielding interlayer honeycomb material.
Example 4
Similar to example 1, a manufacturing technique of graphene/ferrite electromagnetic shielding foam is characterized by the following design and preparation steps (fig. 1-3):
(1) 0.5-5g of graphene, 1000-2200g of deionized water, 50-600g of ferric chloride, 30-200g of ferrous chloride and 10-100mL of ammonia water;
adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; adding the ferric chloride and the ferrous chloride in parts by weight into the graphene suspension, and continuously stirring in a water bath at the temperature of 30-80 ℃ for 10-60 minutes; then adding 10-100g of ammonia water in parts by weight, and continuing stirring in a water bath for 10-60 minutes; and repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral.
(2) Separating the graphene/ferrite particles from the deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%.
(3) Selecting non-woven fabrics as a fabric carrier, paving the non-woven fabrics at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with the deposited graphene/ferrite particles.
(4) And (3) uniformly placing 4 layers of carbon fiber prepreg and 1 layer of high-temperature adhesive film on two sides of the electromagnetic shielding fabric of the graphene/ferrite particles by using a press, and pressing into a hard thin plate.
(5) Processing two vegetable fiber honeycomb sheets, taking the graphene/ferrite hard thin plate as an interlayer material, and bonding the honeycomb and the graphene/ferrite interlayer material by using a high-temperature adhesive film to form the honeycomb interlayer material with the electromagnetic shielding performance.
(6) And (3) designing the number of interlayers according to the electromagnetic shielding requirement, and repeating the step (4) and the step (5) on the basis of obtaining the single-layer graphene/ferrite electromagnetic shielding honeycomb core material to realize the preparation of the multi-electromagnetic shielding interlayer honeycomb material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention should not be limited thereto, and any person skilled in the art should be considered as the technical solution of the present invention and the inventive concept thereof, which are equivalent to or changed by the present invention, within the technical scope of the present invention.
Claims (7)
1. A preparation method of an electromagnetic shielding honeycomb core material is characterized by comprising the following steps:
(1) preparing the following raw materials in parts by mass for later use:
0.5-5 parts of graphene, 1000 parts of deionized water and 2200 parts of Fe3+50-600 parts of Fe2+30-200 parts of ammonia water and 10-100 parts of ammonia water;
preparing graphene/ferrite particles by a hydrothermal method comprising: adding the graphene in parts by mass into deionized water, and dispersing for 0.5-5 hours at the temperature of 30-80 ℃ by using an ultrasonic disperser; mixing the above parts by mass of Fe3+，Fe2+Adding the graphene suspension into the graphene suspension, and continuously stirring the graphene suspension in a water bath at the temperature of between 30 and 80 ℃ for 10 to 60 minutes; then adding 10-100 parts of ammonia water by mass, and continuing to stir in a water bath for 10-60 minutes; repeatedly washing the graphene/ferrite particles by using deionized water until the graphene/ferrite suspension is neutral;
(2) separating the graphene/ferrite particles from deionized water by using a magnet, and preparing graphene/ferrite slurry with the water content of 10-45%;
(3) spreading a fabric carrier at the bottom of a glass container, pouring graphene/ferrite slurry with the water content of 10-45% into the container, placing a strong magnet below the container, depositing graphene/ferrite particles on the fabric carrier, removing excessive water, and drying to obtain the electromagnetic shielding fabric with the deposited graphene/ferrite particles;
(4) sequentially placing adhesive films and prepreg on two surfaces of the electromagnetic shielding fabric of the graphene/ferrite particles to be pressed into a hard thin plate;
(5) the adhesive film is used for bonding the graphene/ferrite hard thin plate between the two honeycombs to prepare the honeycomb sandwich material with the electromagnetic shielding performance, so that the prepared honeycomb sandwich material has the structural characteristics of a honeycomb core material and the electromagnetic shielding function and is a structural and functional integrated sandwich material.
2. The method for preparing the electromagnetic shielding honeycomb core material according to claim 1, wherein the number of layers of the prepreg placed on the two sides of the electromagnetic shielding fabric of graphene/ferrite particles is symmetrical or asymmetrical when the hard sheet is pressed.
3. The method for preparing the electromagnetic shielding honeycomb core material of claim 1, wherein the honeycomb core material is aramid paper honeycomb, plant fiber honeycomb or glass cloth honeycomb.
4. The method of claim 1, wherein the thickness of the single-layer honeycomb is 5mm to 600 mm.
5. The method for preparing an electromagnetic shielding honeycomb core material according to claim 1, wherein the fabric carrier for preparing the graphene/ferrite sandwich material is carbon fiber cloth or non-woven fabric.
6. The method for preparing the electromagnetic shielding honeycomb core material according to claim 1, wherein the prepreg for preparing the hard sheet is a carbon fiber prepreg, a glass fiber prepreg or a plant fiber prepreg.
7. The method for preparing the electromagnetic shielding honeycomb core material according to claim 1, wherein the step (4) and the step (5) in claim 1 are repeated according to electromagnetic shielding requirements to prepare the multilayer electromagnetic shielding honeycomb sandwich material.
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| CN110430741B (en) * | 2019-08-09 | 2021-09-07 | 北京航空航天大学 | Electromagnetic shielding material and preparation device and preparation method thereof |
| CN111154228B (en) * | 2020-01-15 | 2022-12-09 | 深圳市法鑫忠信新材料有限公司 | Preparation method of electromagnetic wave shielding film |
| CN112331375B (en) * | 2020-11-23 | 2022-09-20 | 四川玄武岩纤维新材料研究院(创新中心) | Fiber honeycomb fabric nuclear shielding composite material and preparation method and application thereof |
| CN116696142B (en) * | 2023-08-03 | 2023-10-03 | 晋江市高威电磁科技股份有限公司 | High-strength composite shielding material for manufacturing large electromagnetic shielding command tent |
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